Vinsol-epoxy compositions



' epoxide resin compositions.

.United States Patent- VINSOL-EPOXY COMPOSITIONS Francis E. Reed, Louisville, Ky., assignor to Devoe & Raynolds Company, Inc., a corporation of New York No Drawing. Filed Nov. 10,1958, Ser. No. 772,733

Claims. (Cl. 260-24) The present invention in one aspect relates to new In another of its aspects the invention relates to coating compositions which can be used in the coating of metals, for instance can coatings and the like. In another aspect very satisfactory laminates are prepared using the epoxide resin composition of the invention. In still another aspect the coatings are I suited for coating wires, particularly electrical wires.

The particularly economical epoxide resin compositions of this invention are liquid mixtures of epoxide resins, more specifically ethoxyline resins, with a natural resin known to the trade as Vinsol.

mark of Hercules Powder Company for a hard, brittle, non-tacky, high-melting, thermoplastic material which appears black in reflected'light and which is ruby red when viewed by transmitted light through thin' sections.

It is an extract of pine wood, such as southern pine, particularly the stump, and is comprised of a complex m1xture of acidic materials derived from rosin acids and oxidized rosin acids,- neutral high molecular weight compounds, and acidic phenolic materials in the form of substituted phenolic ethers, polyphenols, and other high" molecular weight phenols. It is gasoline-insoluble and aromatic hydrocarbon-soluble; is saponifiable and esterifiable with polyhydric alcohols; and has an acid number of 90 to 105. Typical analysis values for it are: saponi; fication number 165; methox-yl (OCH content (ASTM or AOAC) percent 5.3; density (at 25 C.) 1.218;

softening point 110 C.' minimum, 125 C- maximum; I gasoline soluble, 20 percent maximum; and toluene insoluble, 25 percent maximum. 7

Epoxide resins with which this invention is concerned include monomeric, or straight chain polymeric epoxy ethers, esters and oils having molecular weights of 250 to 8000. Particularly suited are the ethoxyline resins.

The term ethoxyline resin denotes the well known resins prepared by the condensation of an epihalohydrin with a polyhydric alcohol or phenol with subsequent dehydrohalogenation using a caustic alkali. The term also includes high molecular weight epoxide resins prepared by reacting low molecular weight ethoxyline resins with polyhydric phenols. Thus, as well known in the art, ethoxyline resins are made by condensing glycerol di- Vinsol is a trader @Pftented 6 Not only is Yinsol a solid, but most of the ethoxyline resins also are solids. Accordingly in carrying out this invention it is generally the practice to combine the two usingone or more solvents as a vehicle, sufiicient-solvent being used to give the desired consistency to the .Vinso1-,

' epoxide composition. :Thus a solution of Vinsol in-xylene is mixed with a solution of an ethoxyline resin in methyl isobutyl ketone'. It is known that Vinsol is soluble in a solvent at least as strong as aromatic hydrocarbons, such as xylene, toluene, or benzene. Mixturm of solvents can also beused.

Epoxide resins require a stronger solvent, than does Vinsol, that is a solvent with a greater solvency power for organic compounds, particularly polymers. Suitable ethoxyline resin solvents are the known oxygenated solvents, such as ketones, esters, alcohols and ethers, for instance methyl isobuytl ketone, acetone, butanol, ethyl acetate, butyl acetate .and the diethyl ether of ethylene glycol. If it is desired [to have the same solvent in each solution, orif'it is desired to dissolve first the Vinsol and then the ethoxyline resin, or vice versa, in one solvent, an oxygenated solvent'should be used.

In addition to the Vinsol, the ethoxyline resin and the vehicle, the compositions of this invention can contain agents for more rapid setting or curing of the coating. The agents which effect cross-linking in the ethoxyline resin are desirable and include polyfunctional primary,

' secondary or .tertiary amines such as ethylene diami-ne,

diethylene triamines, 'tetraethylene pentamine, diethyl amine, and the tri(dimetlrylamino methyl) phenols.

However, organic acids, amine salts, amides and BF complexes can be used, for example phthalic acid or anhydride, dicyandiam-ide, and BF, monoethylamine. Urea,

melamine and phenol-formaldehyde resins can' also be used as cross-linking agents. The cross-linking agents can be used in various amounts although they are usually employed in the range oi 0.05 to 10 percent byweight based on the total composition. The amount of crosslinking agent necessary generally depends upon the particular agent. Thusanhydrides and urea-aldehyde resins are, generally used-in greater quantities within the above range than the amines or quaternary ammonium salts.

More than optimum amounts can, of course, be used but there will be no particular advantage in so doing,

Many cross-linking agents react with epoxide resins at roomtemperature. Accordingly the temperatures at which films or laminates of theYinsol-epoxide are cured depend upon the cross linki-ng agent.

from 40 F. to 450 F, Fihns of the composition of V chlorohydrin or epichlorhydrin with ethylene glycol, di-

" ethylene glycol, glycerol, diglycerol, catechol, resorcinol, a tri-hydroxybnezene, a di(hydroxyphenyl)methane, a

di(hydroxyphenyl)ethane, a di(hydroxyphenyl)propane,-

dihydroxydiphenyl sulfone, etc.

US. Patents 2,581,464; 2,582,985; 2,615,007; 2,615,008; 2,698,315; and 2,731,444 describe examples of ethoxyline resin compositions which can be employed in the practice of this invention. By reference the aforementioned patents are intended to be included as a part of the present description of the ethoxyline resins, and for brevity the ethoxyline resin willnot be described other than as a polyether having'terminal epoxide groups on vicinal carbon 7 atoms, and a weight per epoxide group of 140 to 4000.

'- viscosity to a workable consistency. Pigments if em- Temperatures will range the invention-comprise 5-to 40 parts Vinsol and 9 5 to 60 parts epoxide resin based on parts by weight of the Vinsol-epoxide content. .Solvents, diluents and the like are incorporated in amounts sufficient to reduce the ployed are used in accordance with known methods.

The invention is further illustrated by the following specific data and examples. It is understood, however, that the examples are for the purposes of illustration and are not intended to limit'the invention. In the table and examples the epoxide-resins will be designated .byletter,

'e.g.'.'Epoxide A, the resins being described in thelfollow- I -ing table The table shows theratio of epichlorhydrin 'to bisphenol used'to preparethe epoxide resins and gives the epoxide equivalency of the'epoxides'used.

Films prepared in the following examples were .tested -for :hardness; impaet resistance, J conical mandrel bend, 1 adhesion; and boiling" water resistance.

The ratingsaof :each test' appcaring'imthe examples or tables= are as follows:

.IMPACT TEST Rating of'lO-No failure 80inch. lb. Rating of 1-Film'striated*by:cracks but not removed I from steel on '10 inch'lb; impact.

Rating of 'Film removed'jby- 10t1'n'ch 'lb. impact.

CONICAL' BEND Rating of. 10No.cracking.' for. total width. of panel. Ratingof- 7.8Film cracked a-distance of 1%, inches. Rating. of: le-Film. cracked: a: distancejof 2 /2, inches.

.. Rating ofv flaked. from. steel. across. .thethend.

jADHESION-"-KNIFETSCRATCH 'I'hese;.are rated comparativelybased on a rating-0f :zero .(0) :as the :ty eofi-adhesion that allows. a film to .xstrip orfiake ofizaheadof the: knife edge or be removed with a practically -no resistance.

.Example 1 To'-42.3l"partsof a 100*percent non-volatile liquia "epoxide resin -A'are added 37.95 parts of a Vinsol-solu tion, in which 60 parts of-Vinsolare dissolved in a mixture-of 13.57 parts of methyl'isobutyl ketone, 13.5 parts ofn-butanol and 13 parts of xylene. To this epoxide- '"Vinsol'mixture are added"14.'32-parts of a s'olution of a BFg monoethylamine complex made by dissolving 2 parts of the" BF; complex in a mixture of 6.10 parts of'xylene, 5.80 parts of n-butyl acetate', 2.l0- parts of methyl ethyl ketone," and 5.40'parts'of-methyl-isobutyl-ketone. *Also added are 5.42 parts of a butylated urea-formaldehyde resin'made by dissolving 60 parts of the urea-formaldehyde resin in a mixture of 35 parts of butanol-and 5 parts of xylene. Films are prepared'by spraying the-re- "sulting solution onto -24 gauge, No. 160 Bonderized steel panels to form a 2.0-niil'-film. The'films after being cured by baking thirty minutes at 350 F; have the following properties: pencil hardness, 6H;'impact resistance, l0; resistance to conical mandrel bend, 10; resistance to knife scratching, 4; and good-resistance to boiling water. The films after being cured by baking-fifteen minutes at 400 exhibitedpencilhardness, 5H; impact resistance, 10;

resistance to conicalimandrel bend; 10; resistance to knife scratching, 4; and goodresistanoe to boiling water.

Example. 2

In accordance'withgExample 1,261.26 parts, of a resin solution .made by dissolving175 parts of-epoxide resin B in 25 parts ofa mixture madeup of 16.25 parts ofmethyl risobutylvketonezand 8.75mparts1of xylene-.are added to ..32.83' parts of a Vinsol. solution prepared rasinExample 1. .To this? resulting.umixturewarecadded 5.91;.parts of :2,4,6-tri(dimethyl amino methyl)phenol. Filmsprepared as.1in .Example 1-v afterz1being. cured: byi -baking thirty :iminutes'ae 3.00Z-:'F.. have .the.following ..pr operties: pencil *4 hardness, S-H; impact resistance, 10; resistance to conical mandrel bend, l0; resistanceto knife scratching, 4', and good resistance to boiling water.

Example 3 In the manner described in Example 1, 58.04 parts of epoxide resin B solution prepared as in Example 2 are added to 8.13 parts of a Vinsol solution prepared according to 'E-xample 1. To this resulting mixture are added 29.80. parts of a methylenedianiline solutionmade by-dissolving 5J.8.parts1of.methylenediahilinein a mixture of 7.25 parts of n-butyl acetate, 3.375 parts of methyl ethyl ketone, -6.75. parts. 0f methyl =isobutyl ketone, and 7.625 parts of xylene. Also added-are 4.03 parts of the butylated urea formaldehyde resin described in Example 1. Films prepared according to Example 1 after being cured by baking thirty minutes at 300 F. have: a

pencil hardness-of 4-H; an impact. resistance of 10; a

resistanceto a conical. mandrelbend of 10; a resistance to knife scratching of ,5;-and good resistance to boiling water.

. Example -4 "Following Example 1, 33.25 parts of a 100 percent non-volatile-liquid-epoxide'resinA are added to 2.92 parts of'a' Vinsolsolution prepared as in Example 1. To this resulting mixture are added 63.83 parts of a dicarboxylic anhydride solution made by dissolving 50 parts-of 1,4,5,

6,7,7 hexachlorobicyclo (2,2,1)-5-heptene-2,2-dicar- "boxylic anhydride-in"25 partsbf toluene and 25 parts i or isopropyl alcohol. "in Example 1.

Films are prepared as described The filmsare cured by baking fifteen minutes at 400 F.,-producing a hard, tough film.

. Example 5 "In accordance with Example 1, 26.23 parts of a 100 percent non-volatile liquid epoxide A are addedto 23.75 "parts of a Vinsolsolution prepared according to Example prepared as outlined in Example 1.

1. Tothis resulting mixture are added 50.20 parts of "the 1',4,5',6,7,7-hexachlorobicyclo-(2,2,1 -5-heptene-2,3-dicarboxylic anhydride prepared in Example 4. Films are The film is cured bybaking fifteen minutesat400" F., producing a hard Example 6 Foll'owing the procedure of Example 1,.55.08 parts of na'resinlsolution made. by;dissolving 65 parts of epoxide resin C in 35 parts of methylisobutylketone are added 1 to. 23.5 8zparts of the Vinsol solution-dcscribed in Example 1. Tozthis resultingmixturearc added 16.62 parts of the 1,4,5 ,6,7,7 .hexachlorobicyclo(2,2,1 )-5 -hcptene-2,3-dicarboxylioanhydride prepared in Example 4. Also added are 4.72 parts of'the butylated urea-formaldehyde resin. Films are'prepared as in Example 1. The film is cured byubaking fifteenminutesat-400" F., producing a hard -Efilm:showing ,strong'resistance to. boiling water and knife .-scratching.

Example 7 According to the procedure of Example 6, 73.92 parts of epoxide resin C are addedrto 20.07 parts 'of the Vinsol solution described in Example: 1. Tothis resulting mixture is added 1 part of, a quaternary ammonium compound, made bytdissolving 40 parts of benzyl tri-methyl ammonium methoxidel in 60parts of methanol. 'Also added-are. 5.01 parts of the. butylated;.urea-formaldehycle resin described in .Example 1. T Films prepared in accordance1with Example 1. and-cured by baking thirty min- :utes 'at-350. F., are hard films showinggood-resistance to boilingr water K andyknife: scratching, and having a 1 pencil ,1; hatdness:of 44H.

,: Properties .of other films prepared'raccording to, the

. foregoing examples .are. :bestshown in Table, .A, .thefilm forming compositions being .preparedtrom the following TABLE A i Composl- Curing to Pencil Impact Conical Adhesion on F. hardness resistmandrel knife Boiling water test ence bend scratch 30 300 4-H 1 l 4-5 17% hrs-Isolated pin points and slight a 30 @360 411-511 1 10 4 Wi ma-Isolated pin points, and slight 1 p OODL-Qi" 16 @400 4H t 1 10 4 17%flhrs-Isolated pin points and slight oom. 15 @400 6H '10 v. 10 H5 148 hrs-Scattered pin points and rust b i points, slight bloom. 30 350 411 I 7-8 47- 5 148 hrs-Scattered pin points and rust V points, slight bloom; s s

400 611 10 1O 7 148 hrsScattered pin points and rust c points, very'slight bloom.

'30@350 6H '10 10 7 148 hrs-Isolated pin points and rust points, very slight bloom. l5 400 GB 10 10 6-7 148 hrs-Scattered pin points and rust 1i pointsyvery slight bloom and dulling.

@350 6H 10 10 6-7 148 hrs.-Scattered pin points and rust points, very slight bloom and dulling. 30 300 4H 10 10 6 148'hrs-Isolated pin points rust points,

a definitebloom slight dullmg. p v

30 350 511 1 10 4-5 148 hrs-Isolated pinpoints, rust points, t

- definite bloom, slight dulling. l5 400 611 l-2 10 4-5 148 hrs-Isolated pin points, rust points,

' pronounced bloom, slight dulling. I f 30 300 4H 1 4 5 76 hrs-Isolated pin points, rust points, definite bloom and line checking.

. l5 400 2H-3H 1 1 4 76 hrsGenerally flue pin points, rust a points, pronounced bloom, dull, checkmg. p

30 350 2H 1 1 4 62 hrs-Generally fine pin points, rust points, definite bloom, pronounced dulling, checking.

' reactants, the parts being by weight on a solution basis rather than a'solids basis if a solution is used.

Composition a: Parts Epoxide C solution of Example 6 64.33 Vinsol solution of Example 1 23.24 Dimethyl formamide 11.15

Tetraethylene pentamine 1.28

Composition b: v

Solution made by dissolving 40 parts of epoxide D in 60 parts of ethylene glycol monoethly ether acetate 73.60 Vinsol solution of Example 1 12.30 Monoallyl ether of dimethylol phenol 11.03 The butylated urea-formaldehyde resin of Example 1 3.07

Composition 0:

Epoxide D solution of composition b 63.02 Vinsol solution of Example 1 14.01

50 percent solids phenol-formaldehyde resin 20.17 The butylated urea-formaldehyde resin of Example 1 2.80 Composition d Epoxide D solution of composition b 77.57

Vinsol 9.13

ether and 15 parts of xylene 76.38 Vinsol solution of Example 1 8.99 Dimethyl formamide 14.38 Tetraethylene pentamine .25

Composition 1:

Epoxide E solution of composition c 42.27 Vinsol solution of Example 1 37.65 Epoxide A 16.91 2,4,6-tri(dimethyl amino methyl)phenol 3.16

' Composition g:

v .Pants Epoxide B solution of ExampleZ :45.53 Vinsol solution of Example 1 -1 24.37 A dicarboxylic anhydride solution made by dissolvirig SO parts of l,4',5,6,7,7-hexachlorobicyclo (2,2,1)-5=heptene-2,3-dicar- .11 boxylic anhydride in 50 parts of a mixture made up of 25 parts of toluene and 25 parts 1 v of isopropyl alcohol l'.'l 26.03

' The butylated urea-formaldehyde resin of Example 1 4.07

As shown by the foregoing examples excellent fihns result from operation in accordance with this invention. Very satisfactory laminates are also possible according to the practice of this invention as shown in the following example.

Example 8 A pre-preg is prepared by impregnating glass cloth (-Volan A-18l) with a mixture of 25 parts Vinsol and parts epoxide resin A. The Vinsol is employed as a 35 percent solution in acetone and the epoxide resin is employed as a 75 percent solution in methyl isohutyl ketone. The pre-impregnated glass cloth is then heated at 285 F. for twenty minutes to drive out the solvents. A laminate is then prepared by curing twelve plies of the pre-preg for thirty minutes at 340 F. and a measured 200 lbs.

per square inch. The laminates which are then post cured for two hours at 400 F. exhibit the following flexural strengths (ASTM D790-49T): 81,464 p.s.i. at 72 F.; 72,321 p.s.i. at F.; and 23,103 p.s.i. at 200 F. A similarly prepared and post cured laminate without the Vinsol has the following flexural strengths: 80,784 p.s.i. at 72 F.; 68,545 p.s.i. at 150 F.; and 43,740 p.s.i. at 200 F. Similarly determined flexural strengths of laminates containing 35 percent Vinsol, as 'well as room temperature-determined flexural strengths of 25 percent and 35 percent Vinsol laminates, show 25 percent Vinsol to be about the optimum level insofar as physical properties of laminates are concerned.

It is understood that while glass cloth is used in the example the invention is not limited thereto, but to other tos and the like. It is noted also that the compositions complexes and polycarboxylic anhydrides wherein the of the invention can contain pigments, fillers and other Vinsolis present in an amount of 5 percent to 40 percent additives depending upon theirultimateuse:-9ther-modi- ---f-theV insol'ethoXyline-resimmixture.

fications or variations will also occur to one skilled in i4: The coating, compositionwof; claim' 3 wherein the the art and such modifications can be made'withouf'de- 5 cross linking zagent isran amine.

parting from the spirit and scope.ofcthis invention. 2' 5; Thetcoating tcompositionrofz.claim 3 wherein-the What is claimed is: cross-linking agent is an amide.

1. A composite article comprising at'uleast; tW0tcc16-' s .65. The; coating. composition of. claim" 3 wherein the ments adhered together by a thinlayerioi a .curedcorn- :cross-linking agent -is a boron. trifluoride-amine complex. position containing as its sole reactive ingredients VinsDkulO E 7. The: coating composition of: claim 3 wherein the a dark colored, hard, pine resinwhich'issolublein'arocross-linking agent is a polycarboxylic acid anhydride. matic hydrocarbons, substantially insoluble in petroleum 8, Theg coating compositign f l im-r 3, wherein h hydrocarbons and has an Midi-numberedr9oltim5aliiindl cross-linking agentiis an urea-formaldehyde resin. an ethoxyline resin selected from the group consisting"; I 9. The; coating composition of claim3 includingapolar of monomeric and straight chain polymeric (epoxy: 'ethers,';';-:15 solv t, esters and oils having moleculap weights ofi 250 to 8,000, 110. Thecomposition of claim 9-comprising from 95 and at least one of the ethox-yline ,resin cross-linking :to .75 parts of a glycidyl polyether ofapolyhydric phenol agents, urea and melamine-L'aldehyde resins; amine having anepoxy equivalency greater, than one;- 5 to amides, boron trifluoride aminecomplexes-andpolycarparts vi g l b d on 100 paptslby i h of vj lboxylic anhydrides. LZO--polyether content, 'Vinsol comprising a dark colored,

2- A ire Coa W a curedcomposition-containing vhard, pineresin which is:soluble in aromatic hydrocaraS its $016 reactive ingl'edifllts Colored, bons, substantially.insolublein petroleum. hydrocarbons, hard, pine resin which is soluble inrfitOHlflliQ hydrocarnd h an id n b f 90 105; fro 11 to 10 bolls, Substantially insoluble iflPetmkum-hydfmarbons percent ofsaid cross-linking agent based on the Vinsoland has an acid n mber of 9010 1 w fl' y- -polyethen component; and .snflicient solvent to give the resin selected from the group consisting of monomeric d i d consistency to id composition and straight chain polymeric epoxy-etherspestersandoils having molecular weights of 250 to 8,000, and' at least one of the ethoxyline resin cross-linking agents, urea and melamine aldehyde resins, amines, amides, boron trifluoride amine complexes and polycarboxylic anhydrides.

References Cited in the file of this patent UNITED STATES PATENTS A i I 2,732,367 Shokal Jan. 24 1956 3. A coating composition contarmngras 1ts: sole;reacitive ingredients Yinsol;aidark: co1ored;,hard, pine re in 2856094 Gloyer' et a1 58 which islsolubler in aromatic: hydrocarbons,substantially insolublesinpetroleumahydrocarbons .andxhasan acid i FOREIGN PATENTS numbenzof to ,and an ethoxyline :resin selected Canada 1956 from. the group consisting: of monomericand straight chain polymeric ,epoxyvethers, :esters and oils having molecular-weights of 250. to 8,000,-and at leastone of the "OTHER- REFERENCES Austinz' Epoxy Modified Rosin Esters, Paint Oil and ethoxyline resin cross-linkingagents ureaand melamine-40 Chem. Rev., 8 111116 aldehyde resins; amines, amides, boron ti'ifluoride amine 1954- 

1. A COMPOSITE ARTICLE COMPRISING AT LEAST TWO ELEMENTS ADHERED TOGETHER BY A THIN LAYER OF A CURED COMPOSITION CONTAINING AS ITS SOLE REACTIVE INGREDIENTS VINSOL, A DARK COLORED, HARD, PINE RESIN WHICH IS SOLUBLE IN AROMATIC HYDROCARBONS, SUBSTANTIALLY INSOLUBLE IN PETROLEUM HYDROCARBONS AND HAS AN ACID NUMBER OF 90 TO 105, AND AN ETHOXYLINE RESIN SELECTED FROM THE GROUP CONSISTING OF MONOMERIC AND STRAIGHT CHAIN POLYMERIC EPOXY ETHERS, ESTERS AND OILS HAVING MOLECULAR WEIGHTS OF 250 TO 8,000, AND AT LEAST ONE OF THE ETHOXYLINE RESILN CROSS-LINKING AGENTS, UREA AND MELAMINE ALDEHYDE RESINS, AMINES, AMIDES, BORON TRIFLUORIDE AMINE COMPLEXES AND POLYCARBOXYLIC ANHYDRIDES. 